Apparatus for chlorination.



F. SPARRE & W. E. MASLAND.

APPARATUS Fok CHLQRINATION.

APPLICATION FIL-ED AFR. l?. 1913.

' f y MQW mnizzm i F. SPARRE L W. E. MASLAND. APPARATUS FOR cHLonlNATsoN. APPLICATIONVFILED APR. 17. |913.

gllBQQ. l I Patented July 2, 1915.

3 SHEETS-r-SHEET 2.

PPARATUS FOR CHLORINATION.

APPLICATION FILED APR.!7|1913.

Patented July 27, 1915.

3 SHEETS-SHEET 3.

MUTE@ STATES OFFICE.

EEN SPARRE AND WALTER E. MASLAND, OF WILMINGTON, DELAWARE, AS'SIGNORS T0 E. DU PONT DE NEMOURS POWDER COMPANY, OF

CORORATIGN OF NEW JERSEY.

WILMINGTON, DELAWARE, A.

APEA'BATUS FOR lGHLOBLlhTAI'ION.

original application ed ctober 31, 1912, Serial No 728,887.

Specification of Letters Patent.

Patented July 27, 1915.

Divided and this application led April 17,

1913. Serial N0. 761,761.

. 6.- lowing 1s a ull, clearfand exact description thereof.

(ur invention relates particularly to an apparatus for chlorination of saturated hydrocarbons. although it is applicable also to the chlorination of many other coinpounds.

The object of our invention is to provide an apparatus of the kind above referred to, in which the process of chlorination may be carried out continuously and withl a great degree of rapidity, but with safety.

I-litherto, the process of chlorination has l been ordinarily carried out by passing chlo-A rin into a receptacle part-ly filled with the h vdrm-arbons, and subjecting the same to the action of chlorin carriers such as iodin, or to light, or both, in such a way that free spa-ces have been present over the body of liquid, thereby allowing the accumulation of gasesover the surface of the liquid, or thel reaction has been even conducted between the gases themselves. It has been found that hen carried out in this manner the process frequently resulted in an explosion, owing to the fact that the reaction is elfected at times very rapidly, and when a reaction takes place rapidly between two` gaseous constituents-it is likely to result in an explosion.

Our invention comprises an apparatus which will giw better yields, a better control of ope1ations,fand avoid the Apossibility of such explosions. In accomplishing this' result, we cause the chlorin to be absorbed in the hydrocarbons in a dark chamber. Inasmueh a's the reaction between the chlorin andthe satin-ated hydrocarbon takes place, only inthe presence of light, it will be seen that the absorption is effected under conditions which will avoid any reaction between ille ehlorin and the hydrocarbon. Under these eircunistances, there cannot be any cause for an explosion during-the absorption of the chlorm, as the exploslons which arranged as to avoid the have hitherto taken place have been due to conditions which vhave permitted a violent reaction between the chlorin and the hydrocarbons. The chlorin having been absorbed by the hydrocarbons, the liquid is then conducted to a chamber in which it is subjected to the action of light. This chamber is so presence of appreciable free spaces above the body of the liquid. So long as the reaction is eiected Vwithin the body of the liquid, the danger of an explosion is eliminated, as the reaction could not, by any possibility, take place so violently or` with local heating to the ignition point within the body of the liquid as to result in an explosion. The reaction within the chamber referred to is carried out with a great degree of rapidity as we use, in connection therewith, sunlight or a source of blue light which has been found to be the most active in effecting the chlorination. v Furthermore, the reaction is carried out without the necessity of any additional reagents and without the presence of any chlorin carriers such, for example, as iodin or sulfur. In fact, we have discovered that ehlorin carriers are disadvantageous in effecting the reaction, owing to 'the possible danger in their action and difficulty irrecontrolling the process. The process is, fur thcrnioie, carried out in such a manner that there are no mechanical losses, the hydrochloric acid produced in the reaction being recovered and any chlorin and hydrocarbon vapors that escape during the reaction being returned and utilized. The process is, furthermore, carried out in an apparatus in which it can be readily regulated and with ka minimum amount of labor. In operating -v elevation of the apparatus shown -ln Flgs.`

kinds of apparatus for carrying out ourjn vention, for the purposes of illustration and as a preferred embodiment of the ap- .paratus which may be used, we have shown 1 and la; Fig. 3 is an end elevation of the entire plantv con-taining said `apparatus,

' showing the parts somewhat diagrammatically; and, Fig. 41s a plan viewof a portion of the same.

ln the drawings we have shown an opaque `tower 1 having any suitable interior construction to effect the absorption of' a gas in a liquid. This absorption tower has an Vinlet 2 at its top for liquid hydrocarbon, said inlet being connected to a discharge pipe 3` leading from a stoneware plunger pump 4 which withdraws the liquid from a tank 5 by means of a pipe 6. rihe tank 5 is charged with liquid through a lead funnel 7 connected to a stoneware stop-cock 8 supported'in 'the outer end of an inlet pipe 9, leadinginto said tank. The stoneware pump 4 is operated in any suitable manner to force a continuous current of 4the liquid into the top of the absorption tower 1. Near the bottom of the tower there is provided an inlet pipe 10 for chlorin gas, leading from a series of chlorin bottles 11, containing lliquid chlorin. Stop-cocks 12 are provided on Vthe tops of these bottles topermit the ow of chlorin gas to be readily regulated. The hydrocarbon liquid having absorbed the chlorin gas, it is conducted out ott' A,the tower 1 at its base by means of a glass tube 13 leading .into a stoneware pipe 14. The

pipe 14 conducts the liquid to a' manifold 15,

to which are attached a plurality of inclined glass tubes 16, in order to subject the-liquid to the action of light. The liquid iiowing through the tubes 16 is then. ,conducted through a manifold 17 and by means of a pipe 18 to a manifold 19, another similar set of glass tubes 20, a manifold 21, a pipe 22 similar to pipe 18, a manifold 23, a similar yset of glass tubes 24, and a manifold 25. VAs

the liquid passes through the glass tubes 16,

i 20 and`24, the chlorin. gas becomes combined withthe hydrocarbons, giving ofr" hydrochlori acid, and the process is so regulated that tpe yellow color of the chlorin gas will have disappeared when the liquid has passed out of the lowermost set of glass tubes 24. From the manifold 25, the liquid .is conveyed by a pipe 26 to the tank 5, which may have, a 'glass cover if desired to increase the action df the light and which is provided.

with a raw-oif cock 27 todraw the liquid olf whe the reaction is complete, that is to say, when the hydrocarbons have been suficiently chlorinated. The apparatus is usually operated in such a manner, however, as to circulate the liquid through the absorption tower and the glass tubes referred to until the required degree of chlorination has been effected. Any gas which accumulates in the tank 5, which is principally hydrochloric acid gas, is conducted away by means of a pipe 28. This pipe 28 has connectcd to it a series of branch pipes 29, one of which communicates with each of the manifolds 15, 21 and 23 in order to convey v away from said manifolds any gases which have accumulated during the reaction. The gases which have been thus obtained from the tank 5 and the manifolds 15, 21 and 23 are then conveyed through the pipe 30, to which is connected a pipe 30a, havingr a plurality of branches 30l,.one ofl which leads to each of the manifolds 17, 19 and 25. The gases which have thus been collected in the tank 5 and the various manifolds, are conveyed by means of the pipe 30 to a glass condenser 31 having provision for a water jacket 32supplied with a current of-jcold water by. inlet and outlet pipes 33 and 34. The purpose of the jcondense'r 31 ,is to condense as much ofthe hydrocarbon vapor as possible and to return it to the main body of hydrocarbon liquid. From the condense:` 31 the gases are conveyed by a-pipe 35 to the bottom of an4 absorption tower v36, designed for absorbing the hydrochloric acid gas in water. The tower 36 has any suitable interior .construction for effecting this purposje. The hydrochloric acid gas is conveyed upwardly through said tower and is subjected therein to a current of water which is conveyed downwardly. through the same from an inlet pipe 37 having a funnel 38 to receive a stream of water from a water supply pipe 39. This pipe 37 also has a water jacket 40 to condense as inuch as possible of the condensable vaporswhich fail to be absorbed in the tower 36. The vapors which are not absorbed in this manner are con ducted from the pipe37 in the reverse direction into a vapor collector41 having a water jacket 42 provided with a water inlet). ipe 43 and an outlet pipe 44 for the waste wfifr.' The outlet pipe 44 from the water jacket 42 is connected to. an inlet pipe 45 leading to VV,the water jacket 40 upon the pipe 37, and

' lector 41. is provided with a body of oil tow absorb any ofthe hydrocarbon vapors 'which fail to be condensed in the other portions of the apparatus. Atits end, the vapor' cbllec# tor 4l has a T-joint 47 from thel topof which, avent pipe'48 leads to the outer atmosphere, and ronrthe bottom of the T- joint 47 a discharge pipe 49 leads downwardly to the outer part of the apparatus gas therein, is conducted out of the said` tower by means of a pipe 51, and through aspray nozzle 52 into the tank 5. The liquid containing hydrochloric acid gas and chlorin gas is thus brought into intimate contact with the body of hlorinated hydrocarbons within the'tank 5, and thereby any chlorin present in the water is abstracte by, Iand becomes absorbed in the hydrocarbons. f

Any ,chlbri-n gas which fails to be absorbed b v the hydrocarbons in the absorption tower l' is conducted Jfrom the top thereof by means ota-,pjpe 53 which is inclined upwardly trom-'the top ot the absorption tower to a pipe 54 which conveys the gas through a glass .lantern'.55, a rpipe 56 and a pipe 5 to the tank 5,' where the chlorin is, at least in part, ab orbed by the hydrocarbons in said-tank. The upwardly directed pipe 53 provided with a water jacket 58 to condense ahy hydrocarbon vapors which may have escaped from-.the top of the absorption tower. This waterjacket 58' has a -water inlet pipe 59,. a vent 60, leading to the openyair, and av watr'bvertlow pipe 61 leading; downwardly therefrom tothe sewer.

ln' order to maintain'the tank 5 as cool I as possible, there is a waterspraying pipe 62 located at each side thereof `for spraying water on the sides of the tank. This water spraying pipe is supplied with a stream of water by means of a pipe GS'having a handoperatcd valve G4. The water thus sprayed noon the sides ot' the tank is collected in a trough (l5 surrounding the bottom ot the same, from which an overflow pipe 66 leads to thesewer. `The tank 5 thus acts as an accumulator ot all the liquid products of the apparatus, the hydrocarbons and the chlorinated hydrocarbons collecting in the iop ot the tank, and the hydrochloric acid and water collecting in the bottom thereof. he hydrochloric acid is conveyed Jfrom the bottom ot said tank by an overflow tube 67 leading to a pipe GS, the top of which is open to the atmosphere and the bottom of which leads. by means of a pipe 69, to a. ..tonc\\'arc reservoir 70 for receiving hydrochloric acid. The bottom ot the reservoir To, has a draw-off cock 7l and said reservoir is also supplied with an overflow pipe 72 leading upwardly from its bottom and discharging into a pipc 73, leading to the The various water inlet pipes are provided ith av supply of water from a common water inlet pipe 74 having a branch 75 leada branch 7 6 leading to the 77 leading to the pipe 33, 43, and a pipe Over the glass have located a selights S0 which are blue light upon said ights 8O are 'supported they may be readily t is desired to have sun- The entire osed in a building S1 havthe top and sides thereof the apparatus l ing to the pipe 59,

leading to the pipe 79 leading to the tubes 16, 20 and 24, W ries of mercury vapo adapted to throw a tubes. y The mercury l in such a manner t moved away when i 'lighfthrown up appa atus is incl ass panes 82 at to the portion glass tubes r of ladjacent including the order to control the amou through the glass panes, tain 83 beneath the panes 1 curtain 84 over the p of light coming we provide a eurn the roof, and a the wall of the lation of the curd the lights 80 the proper be thrown upon the tion is to be eti apparatus may be l tains'SB and 84 an degree of li tubes in which the reac The operation of the summarized asfollows: hydrocarbons the pump-4 is st of the hydroca war'dly through speed otthis of operatic t of chlorin is then a s 1:1 by properly ma lves thereon until a proper tted to the absorpmount of chlorin he complete disappearcolor from the hydroleaves the last series of ch as the absorption d to take place in the k chamber, that is to sorption is eecte f chlorination begins.

o danger of an eX- This is very ch as an explosion in the s would be very destruchat the applicants d apparatus ot tion will not take er where there is free space s orvapors. ected the hydrohe absorbed chlorin pass When a quantity o ed in the tank 5, Y arted and a constant stream ons is caused to pass d the absorption t current may n of the pump 4.

dmitted from the nipulating has been plac lated by the chlorin bottle the hand va A amount of chlorin is admi vtion tower, the prop being determined vby ance of the yellow carbons as the same glass tubes 24. of the chlorin is cause carbons in a dar ower l, the before the reaction o There is, consequ plosion during th important, inasmu presence of vapor t is for this reason t e absorption.

have devised a process an a character tha. place in a chamb for the collection of gase absorption having carbons containing t downwardly throng the light, which may the blue light emanati vapor lamps 80, thel hydrocarb nated hydrocarbons are then Any hydrochlori which escapes from the liquid reaction and after the ducted into the tank 5, is conve h theglass tubes where be either daylight or ng from the mercury the chlorination ot' to be eected.v The chloridischarged into c acid gas during the liquid has been conyed by means hydrochloric acid still remaining in solution in the hydrocarbons and chlorhydrocarbons in the tank 5. It Will be understood that the Water containing hydrochloric acid may also contain chlorin gas owing to the escape thereof from the tank 5 or from the various manifolds of the glass tubes in Which the reaction is effected. Some of the chlorin thus conducted into the/absorption tower 36 may also have emanated from the top' of the absorption tower 1 from which the unabsorbed chlorin gas is led by means of a series of pipes into the'top of the tank 5. The liquid which is thus conveyed from the bottom of the tower 36 into the tank 5 may 'also contain' any liquids condensed beyond the`tower 36 in the condenser 40. Any gases Which are not condensed inv the condenser are led into the vapor collector Where the uncondensed hydrocarbon vapors are absorbed inv a body of kerosene or similar hydrocarbons which may be drawn oit from time to time by the pipe 49. Any remaining gasesy or vapors are vented to the outer air by means of the vent 48. From the ta'nk 5 the accumulated Water containing vhydrochloric acid is conveyed continuously to the storage receptacle 70 from which it iiows out continuously from the bottom through the pipe 72. Any hydrocarbons or chlorhydrocarbons carried oil accidentally into the receptacle 70 will remain in the upper part of the same and may be drawn ofi' as desired through the cock 71. The height of the liquid inthe tank 5 vmay be regulated as desired by raising o1" lowering the movable parts 67, 68

and 69. The hydrocarbons and chlorhydrocarbons which .haye collected in the tank 5 are circulated through the tower and the glass tubes in which the reaction takes place,

until the proper degree of chlorination has been eiiectcd. In rthe'rst stages of the operation of the apparatus, -a mixture of monochlorand dichlor substitution products f is obtained, together With some unchanged hydrocarbons. As the treatment continues,

some of the higher substitution products are formed in addition. If it is desirable to obtain only monoand dichl'or substitution products, the .apparatus isl operated until about one-.halfv of 'the hydrocarbons have been chlorinated. The process is then stopped and the chlorinated hydrocarbons While We have described our invention above in detail, we wish it to be understood f that many 'changes may be made therein without departing from the spirit of our` invention.

We claim: f

1. The combination-of a transparent reaction chamber comprising a plurality of glass tubes connected to manifolds, an inlet. for liquid into the same, an outlet therefrom, and means for,preventing the maintenance of a body of gas over the liquid;

2. The combination of a transparent re-v' action chamber comprising a'plurality of glass tubes connected to manifolds, an inlet 'for liquid` into the same, an outlet therefrom, and means for preventing the maintev nance of a body of gas over the liquid comprising Agas vents for the manifolds. 3. The combination' of an opaque absorption chamber, -and a 'transparent liquid reaction chamber and means forv passing a liquid through said chambers.

Vet. The combination of an opaque absorption chamber, and a transparent reaction chamber, means for passing a liquid through said chambers, vand means for Apreventing the maintenance of a body of gas therein, comprising an outlet for gas connected to thehighest point in the chamber. I

5. The combination of an opaque absorption apparatus, a transparent. reaction chamber, and means for circulating a liquid therethrough. i 6. The combination of an opaque absorption apparatus,- a transparent 'reaction chamber, f ,and means for preventing the maintenance of a body of gas therein, and means for circulating a liquidtherethrough.

7. The combination of an absorption chamber for absorbing a gas in 'a liquid, a transparent liquid reaction chamber and-3 mercuryvapor light and meanspfor passing a liquid through the'chambers.

8. The combination ,of an absorption chamber for absorbing 'a gas in a liquid, a.:

transparent liquid reaction chamber,- adapted 4to be subjected to daylight, a mercury.

labsorbed gas for absorption of the l 'gas therein.

10. The combination of a reaction chamber, a receiving chamber attached to the disconducting the recovered gas to the receiv-f ing chamber.

' 11. ,The combination .of a reaction chamber, a receiving chamber attached to the discharge end, 'hereof and means for recover'- ing by absorption inwater gasliberated 'during the reaction and .conducting the Water solution to the receiving chamber,

12. The combination of a vreaction chamber, a receiving chamber-attached to the discharge end thereof, and means for recovering byabsorption in water and condensation 'gas' liberated vduring the reaction and condensation, and conducting the Water s0- lution with the condensed gas to .the receiving chamber.

' 13. The combination of a reaction chamber, a receiving chamber attached to the for recovdischarge end thereof, means for recovering by absorption in Water gas liberated during the reaction and conducting the Water'solution to the receiving chamber, and means for absorbing the residual gas in oil.

let. The combination of a reaction chamber, a receiving chamber attached to the discharge end thereof, means for recovering by absorption in Water and condensation gas liberated during the reaction, and returning the Water solution with the condensed gas to the receiving chamber, and

vmeans for absorbing the residualgas in oil;

vIn testimony that we claim the foregoing we have hereunto set our hands.

FIN SPARRE. WALTER E. MASLAND. Witnesses:

HAMILTON BRADSHAW, ROBERT J. LILLEY. 

